Alkyl-substituted bicycloalkyl ethers

ABSTRACT

Alkyl-substituted bicycloalkyl ether compositions useful in the preparation of synthetic lubricant compositions are obtained by reacting an alkyl-substituted 2-norbornene with a monohydric alcohol in the presence of an acidic catalyst.

BACKGROUND OF THE INVENTION

1. Field of the Invention

This invention relates to new alkyl-substituted bicycloalkyl ethercompositions, and particularly to monoalkyl ethers of alkyl-substitutedbicyclo (2.2.1) heptanols, which are useful in the preparation ofvaluable lubricant compositions, and to an efficient process forpreparing the new ethers in high yields from alkyl-substitutednorbornene compounds.

The invention specifically provides new and particularly usefulmonoalkyl ethers of alkyl-substituted bicyclo (2.2.1) heptanols whichcan be generically represented by the formula ##STR1## wherein R ishydrogen or methyl, x is an integer ranging from 4 to 18, y and z areintegers ranging from 0 to 16 whose sum must be 8-16, and the sum ofx+y+z must be 20 to 36. The invention also provides an efficient processfor preparing the new ethers which comprises reacting analkyl-substituted norbornene with a monohydric alcohol in the presenceof an acidic catalyst.

The new ethers of the invention possess valuable properties which makethem suitable for use in important commercial applications, such as inthe preparation of lubricant compositions. Because of their high boilingpoints, good stability and desired viscosity and lubricating propertiesthe new ethers of this invention are particularly useful in thepreparation of improved lubricant compositions.

2. Prior Art

Some ethers of bicyclo (2.2.1) heptanol have been prepared in the past,such as described in U.S. Pat. No. 3,370,080, by hydrating norbornene toform norbornane alcohol and reacting that secondary alcohol with analkylene oxide. Such products have a polyoxyalkylene group which limitsthe oleophilic properties of the ethers. The oleophilic properties ofthe products of U.S. Pat. No. 3,370,080 are further restricted by thelimitation on the size of the alkyl side chains as noted in thatreference.

Further advantage of the present ether compositions over other types ofknown synthetic lubricant compositions, and particularly those of theester type, include the improved resistance to alkali and hydrolysis ofthe ether linkage over the ester linkages of the known compounds.Additional advantage is also found in the fact that the new ethercompositions can be prepared from inexpensive compounds, such asalphaolefins and cyclic diolefins, and obtained in high yield by asimple two-step process; thus presenting an economic advantage over manyof the known synthetic lubricant compositions.

SUMMARY OF THE INVENTION

The ethers of the present invention comprise the monoalkyl ethers ofalkyl-substituted bicyclo (2.2.1) heptanols and can be genericallyrepresented by the formula ##STR2## wherein R is hydrogen or methyl, xis an integer from 4 to 18, y and z are integers from 0 to 16 whose summust be 8 to 22, and the sum of x+y+z must be 20 to 36. The inventionfurther provides an efficient process for preparing the new ethers inhigh yields which comprises reacting an alkyl-substituted norbornenewith a monohydric alcohol in the presence of an acidic catalyst.

In view of their valuable properties, and particularly their highboiling points, good stability to alkali, and desired viscosity andlubricating properties, the new ethers of the invention are particularlysuited for preparation of lubricant compositions, and the inventionprovides new and valuable lubricant compositions containing the said newethers.

DESCRIPTION OF THE PREFERRED EMBODIMENTS

While R in the above-described formula is preferably hydrogen, it mayalso be methyl.

In the above-described formula x is an integer ranging from 4 to 18yielding alkyl radicals which may be exemplified by butyl, hexyl,isohexyl, heptyl, octyl, dodecyl, tridecyl and tetradecyl radicals, andthe like. Particularly preferred compounds are those wherein the x inthe above-described formula ranges from 6 to 14 and the radicals containfrom 6 to 14 carbon atoms.

In the above-described formula y and z are integers ranging from 0 to 16whose sum must be 8 to 22 with the sum of x+y+z equaling 20 to 36.Examples of hydrocarbon radicals which yield such configurationsinclude, among others, 1-octyl, 1-decyl, 1-dodecyl, 1-ethylhexyl,1-butyldodecyl, 1-amyltetradecyl, 1-propyldodecyl, 1-ethyldecyl,1-hexyldodecyl, 1-heptyloctadecyl, 1-ethyleicosyl, octadecyl,tetradecyl, nonadecyl, eicosyl, 1-hexyldecyl, 1-hexyloctadecyl and thelike, and mixtures thereof. Where branching in the radical is avoided(i.e., when z is equal to 0) unusual properties are imparted to the newethers and such products represent a specially preferred group ofethers.

Particularly preferred ethers are those of the formula wherein R ishydrogen, x is an integer from 4 to 18, z is 0 to 8 and y is an integerfrom 14 to 22, with the total of x+y+z equaling 20 to 36. Also ofinterest are those of the formula wherein R is hydrogen, x is an integerfrom 6 to 14, z is 0 and y is an integer from 14 to 30, with the totalx+y being 20 to 36.

The new monoalkyl ethers of alkyl-substituted bicyclo (2.2.1) heptanolsof the present invention can be exemplified by the following:

5- and 6-tetradecyl bicyclo (2.2.1) heptyl decyl ether.

5- and 6-octyl bicyclo (2.2.1) heptyl tetradecyl ether.

5- and 6-octadecyl bicyclo (2.2.1) heptyl 1-butyldecyl ether.

5- and 6-dodecyl bicyclo (2.2.1) heptyl 1-octyldodecyl ether.

5- and 6-heptyl bicyclo (2.2.1) heptyl 1-dodecyltetradecyl ether.

5- and 6-butyl bicyclo (2.2.1) heptyl 1-tetradecyloctadecyl ether.

5- and 6-octylbicyclo (2.2.1) heptyl 1-amyloctadecyl ether.

5- and 6-dodecyl bicyclo (2.2.1) heptyl 1-octyldodecyl ether.

5- and 6-dodecyl bicyclo (2.2.1) heptyl 1-amyloctadecyl ether.

5- and 6-butyl bicyclo (2.2.1) heptyl eicosyl ether.

5- and 6-octyl bicyclo (2.2.1) heptyl 1-octylpentadecyl ether.

5- and 6-butyl bicyclo (2.2.10 heptyl 1-butyleicosyl ether.

Coming under special consideration are the alkyl ethers of 5- and6-alkyl bicyclo (2.2.1) heptanols wherein the alkyl ether radical andthe alkyl radical substituted on the bicyclo (2.2.1) heptanol moleculetogether contain from 20 to 36 carbon atoms.

The new compositions of the present invention can be prepared by avariety of methods but are preferably prepared by condensing analpha-olefin with a cyclopentadiene or dicyclopentadiene as in aDiels-Alder type condensation reaction to form an alkyl-substitutednorbornene, and then reacting the norbornene with the desired monohydricalcohol in the presence of an acidic catalyst. It was unexpected to findthat the monohydric alcohols could be added to the alkyl-substitutednorbornenes in the presence of the acidic catalyst to form the desiredsubstituted norbornanes in view of certain disclosures in the prior artindicating that related acid catalyzed reactions with norbornenesresulted in many cases in a structural rearrangement. See, for example,Kock et al. Liebigs Ann. Chem. 638. 11 (1960).

The formation of the alkyl-substituted norbornenes by reacting analpha-olefin with a cyclopentadiene or dicyclopentadiene can beillustrated by the following equation: ##STR3## wherein R may behydrogen or an alkyl radical as described above and the --(CH₂)_(x)radical may be as described above wherein x is an integer from 4 to 18.It is well known that the cyclopentadienes are in equilibrium with thecorresponding dicyclopentadienes and the use of the dicyclopentadienes,as in some of the working examples at the end of the specification, isin effect addition of the cyclopentadiene as shown in the aboveequation.

The alpha-olefins used in the preparation of the alkyl-substitutednorbornenes by the reaction shown above may be of any type but arepreferably the 1-alkenes containing at least three carbon atoms, andpreferably from 6 to 20 carbon atoms. Such olefins may be exemplified by1-pentene, 1-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene,1-octadecene, 1-eicosene, 3-butyloctene-1, 2 6-dimethyldodecene-1,3-amyldodecene-1, and the like, and mixtures thereof. These olefins arepreferably obtained by cracking hydrocarbon wax or by telomerizingethylene.

The reaction between the alpha-olefin and the cyclopentadiene ordicyclopentadiene to form the alkyl-substituted norbornene as shown inthe above equation can be accomplished by heating the componentstogether in a sealed autoclave at a temperature generally ranging fromabout 150° C. to about 300° C., and more preferably at about 200° C. Thepressure may vary as needed to help the reagents in the liquid state atthe temperature selected and generally will range from about 1 to about20 atmospheres. The components can be combined in a variety of differentratios varying from stoichiometric amounts up to an excess of eitherreactant. In general, it is preferred to utilize the alpha-olefin inlarge excess, e.g. from 2 to 6 molar excess. More specifically, molarratios of cyclopentadiene to alpha-olefin may vary from about 1:1 to 1:5as needed or desired. Solvents may be utilized as desired, but in manycases the excess alpha-olefin furnishes sufficient fluidity for thedesired condensation reaction. The desired alkyl-substituted norbornenescan be recovered from the reaction mixture by any suitable means, suchas distillation, solvent extraction, and the like.

In view of the different steric arrangements that may result from thistype of condensation, the resulting products will generally be a mixtureof endo and exo derivatives as represented by the following illustrationof the structure of endo-5-butyl-2-norbornene andexo-5-butyl-2-norbornene: ##STR4## Examples of these mixtures of stericisomers include, among others, a mixture of endo-5-octyl andexo-5-octyl-2-norbornene, mixture of endo-5-dodecyl andexo-5-dodecyl-2-norbornene, a mixture of endo-5-tetradecyl andexo-5-tetradecyl-2-norbornene, a mixture of endo-5-heptyl andexo-5-heptyl-2-norbornene, and a mixture of endo-5-octyl and6-octyl-2-norbornene. These isomers have closely-related boiling pointsand react substantially the same in the formation of the new products ofthe invention so they can be used as a mixture without furtherseparation.

The alkyl-substituted norbornenes prepared as above are then reactedwith a monohydric alcohol to form the desired monoalkyl ether of thealkys-substituted norbornane. This reaction can be illustrated by thefollowing equation: ##STR5## wherein R, x, y and z are as describedabove for the generic formula representing the compounds of the presentinvention.

The monohydric alcohols to be reacted with the substituted norbornenesmay be any primary or secondary monohydric hydrocarbon alcohol havingthe prescribed number of carbon atoms as set out in the generic formula.Examples of such alcohols include, among others, 1-butanol, 2-pentanol,2-hexanol, 1-octanol, 1-ethylhexanol-1, 1-heptyloctanol-1,1-tetradecanol, 1-eicosanol, 1-pentyldodecanol-1, 1-octyloctadecanol-1,1-ethyleicosanol-1, 1, 3, 5-tributyldodecanol-1,1-butyl-2-isohexyltetradecanol-1, and 1-isohexyl-tetradecanol-1, andmixtures thereof. Particularly preferred are the normal alkanols and thesecondary 1-alkylalkanols containing from 4 to 20 carbon atoms.

The reaction is accomplished by heating the alkyl-substituted norbornenewith the monohydric alcohol in the presence of an acidic catalyst. Theacidic catalyst employed may be any of the known Friedel-Crafts or Lewisacid type catalysts. Such catalysts include, among others, borontrifluoride complexes, such as their ether complexes, hydrofluoric acid,aluminum chloride, tin chloride, ion-exchange resins, such as Amberlyst®15, a cross-linked styrene-sulfonic acid resin manufactured by the Rohmand Haas Co., and Nafion®, a polyfluoro carbon supported perfluorosulfonic and resin manufactured by E. I. du Pont de Nemours and Co.,etc., and mixtures thereof. Preferred catalysts include borontrifluoride and its complexes, and particularly its complexes withethers, such as, for example, boron trifluoride diether complex, borontrifluoride dipropyl ether complex, boron trifluoride cyclohexyl ethercomplex, boron trifluoride benzyl ether complex, and boron trifluoridedicyclopentenyl ether complex, and the like, and mixtures thereof.Suitable substitutes include the corresponding boron tribromide andboron triiodide complexes. The amount of the acidic catalyst employedmay vary over a wide range depending upon the catalyst selected,reactants and conditions. In general, the catalyst will vary from about0.01% to 10% by weight of the reactants, and more preferably from about0.1% to 5% by weight of reactants.

The proportion of the alkyl-substituted norbornene and the monohydricalcohol to be used in the reaction mixture may vary over a wide range.In most cases, it is desirable to utilize the above components in aboutstoichiometric amounts although it is sometimes convenient to utilize anexcess of either reactant. In general, reactants are employed in molarratios varying from about 1.5:1 to 1:1.5.

Preferably, the reactants can be combined by themselves, however, inertsolvents or diluents may be utilized as needed or desired.

The temperature employed in the reaction between the substitutednorbornene and the monohydric alcohol may vary over a wide rangedepending upon the catalyst selected, nature of the reactants andreaction rate desired. In most cases, the temperature will vary fromabout 100° C. to 200° C., and still more preferably from 100° C. to 150°C. Pressures may also be varied as needed to keep the reactants in aliquid state at the temperature selected and generally will range fromabout 1 to about 20 atmospheres. It is generally preferred to conductthe reaction in an inert atmosphere, such as in the presence ofnitrogen.

The desired ether products can be recovered from the reaction mixture byany suitable means, such as distillation, solvent extraction, and thelike. Preferably the unreacted components as well as the product arerecovered by reduced pressure distillation, leaving the desired ether asbottoms product.

The alkyl-substituted bicycloalkyl ethers of the present invention willvary from liquids to soft solids and will be soluble in a variety ofsolvents. They possess valuable properties which make them suitable foruse in important applications, such as in the preparation of lubricantcompositions and plasticizing agents. The new ethers are particularlyuseful in the preparation of synthetic lubricants because of their highboiling points, good stability and desired viscosity and lubricatingproperties. In this application, they may be used as such or added ascomponents for other lubricating products, such as other hydrocarbonliquid lubricants or other synthetic polyester lubricant compositions.

To illustrate the preparation of the new ethers and their properties,the following examples are given. It is to be understood, however, thatthe examples are given in the way of illustration and are not to beregarded as limiting the invention in any way.

EXAMPLE I

This example illustrates the preparation and some of the properties of5- and 6-octyl bicyclo (2.2.1) heptyl tetradecyl ether.

1-decene (5984 g) and dicyclopentadiene (770 g, technical grade) wereplaced in a sealed autoclave and heated to 220° C. for a period of about3 hours. The reaction mixture was then distilled to give a mixture ofexo- and endo-5-octyl-2-norbornene.

1-tetradecanol (30.0 g) the mixture of exo- andendo-5-octyl-2-norbornene (88 g) produced above and of Nafion® resincatalyst (5.0 g) were placed in a 300 ml rocking autoclave fitted with aglass liner, under nitrogen atmosphere and reacted at 120° C. for aperiod of about six hours. After cooling to room temperature, thereaction mixture was separated from solid catalyst by filtration. Theunreacted 5-octyl-2-norbornene and 1-tetradecanol were removed bydistillation leaving the 5- and 6-octyl bicyclo (2.2.1) heptyltetradecyl ether as bottoms product. The ether recovered in yield of40.09 grams had a viscosity index of 138. The structure was identifiedby nuclear magnetic spectra. Addition of the ether to conventional lubestock gives a lubricant composition having good stability andlubricating properties.

EXAMPLE II

This example illustrates the preparation and properties of 5- and6-hexyl bicyclo (2.2.1) heptyl octadecyl ether.

1-octene (1400 g) and dicyclopentadiene (280 g, technical grade) werereacted in a sealed autoclave at 220° C. over a period of three hours.The reaction mixture was then distilled to give a mixture of exo- andendo-5-hexyl-2-norbornene.

1-octadecanol (37.8 g), the mixture of exo- andendo-5-hexyl-2-norbornene (32 g) produced above and of Nafion® resincatalyst (5 g) are placed in a 300 ml rocking autoclave as in thepreceding example and reacted under nitrogen at a temperature of 120° C.for a period of about six hours. After cooling to room temperature, thereaction product is separated from the solid catalyst by filtration. Theunreacted exo- and endo-5-hexyl-2-norbornene and 1-octadecanol areremoved by distillation leaving the desired 5- and 6-hexyl bicyclo(2.2.1) heptyl octadecyl ether. Addition of the new ether toconventional lube stock gives a lubricant having improved lubricatingproperties.

EXAMPLE III

This example illustrates the preparation of 5- and 6-octyl bicyclo(2.2.1) heptyl 1-butyldecyl-1 ether.

1-butyldecanol-1 (30 g), the mixture of exo- andendo-5-octyl-2-norbornene (38 g) produced in Example I and Nafion® resincatalyst (5 g) are placed in a 300 ml rocking autoclave and heated undernitrogen for about six hours at 120° C. After cooling to roomtemperature, the reaction mixture is separated from solid catalyst byfiltration. The unreacted 5-octyl-2-norbornene and 1-butyldecanol-1 areremoved by distillation leaving the 5- and 6-octyl bicyclo (2.2.1)heptyl 1-butyldecyl-1 ether as bottoms product.

Addition of the above-described ether to lub stock gives a lubricantcomposition having improved lubricating properties.

EXAMPLE IV

Example I is repeated with the exception that the mixture of exo- andendo-5-octyl-2-norbornene is replaced with equivalent amounts of each ofthe following: exo- and endo-5-decyl-2-norbornene, exo- andendo-5-dodecyl 2-norbornene and exo- and endo-5-tetradecyl-2-norbornene.Related results are obtained.

EXAMPLE V

Examples I, II and III are repeated with the exception that the Nafion®resin is replaced by an equivalent amount of boron trifluoride diethylether complex. Related results are obtained.

I claim as my invention:
 1. Alkyl-substituted bicycloalkyl alkyl ethersof the formula ##STR6## wherein R is selected from the group consistingof hydrogen and methyl, x is an integer ranging from 4 to 18, y and zare integers ranging from 0 to 16 whose sum must be 8 to 22 and the sumof x+y+z must be 20 to
 36. 2. A compound as in claim 1 wherein R ishydrogen, x is an integer from 6 to 14, z is 0, y is an integer from 14to
 30. 3. A compound as in claim 1 wherein R is hydrogen, x is aninteger from 4 to 18, z is 0 to 8, and y is an integer from 14 to
 22. 4.A new composition comprising 5- and 6-octyl bicyclo(2.2.1)heptyltetradecyl ether.
 5. A new composition comprising 5- and 6-hexyl bicyclo(2.2.1) heptyl octadecyl ether.
 6. A new composition comprising 5- and6-octyl bicyclo (2.2.1) heptyl 1-butyldecyl ether.